JPS5910733B2 - Heat-resistant photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-resistant photosensitive material, and more particularly to a photosensitive material that is photochemically cured to provide a heat-resistant substance.

In recent years, demand for heat-resistant photosensitive materials has been high, and they are being applied mainly as protective materials, insulating materials, solder resists, adhesives, coating materials, etc. in the electrical and electronic fields, and as heat-resistant photoresists in the manufacture of semiconductor devices. . This type of photosensitive material is not only required to have excellent photocurability and heat resistance after photocuring as its original characteristics, but also to exhibit good adhesion to adherends.
It is also desired that the material satisfies various properties such as insulation properties, moisture resistance, and chemical resistance.

On the other hand, from the viewpoint of pollution-free, resource-saving, and energy-saving, it has the ability to form a film without any solvent or with a small amount of solvent, and furthermore, there are problems such as gelation of photosensitive materials over time before use. It is desired that the material has excellent storage stability without causing any damage. However, there are few conventional photosensitive materials that satisfy all of these required properties.

In general, those with excellent photocurability tend to have poor storage stability, and many also lack adhesive strength to adherends. From this point of view, the present invention has excellent storage stability, has the originally required good photocurability and heat resistance, and satisfies all of the above-mentioned required properties, including excellent adhesion to adherends. The purpose is to provide a new and useful heat-resistant photosensitive material.

That is, the present invention relates to P-phenylene diacrylic acid or a derivative thereof, and a compound having the following general formula; ↑In the formula, R is a heat-resistant polyesterimide whose main component is an unsaturated polyesterimide obtained by reacting a residue of amino\alcohol with a polyhydric alcohol containing a dihydric alcohol having an imide bond in the molecule. This relates to photosensitive materials.

As described above, the heat-resistant photosensitive material of the present invention contains P as its main component, which has two photopolymerizable carbon-carbon double bonds in the molecule.
- Made by esterifying phenylene diacrylic acid or its derivatives with a dihydric alcohol having an imide bond in the molecule, or by esterifying it in the presence of other polybasic acids or polyhydric alcohols. It uses unsaturated polyesterimide, and this polyesterimide has a specific proportion of imed bonds and photopolymerizable carbon-carbon double bonds in the chain molecule, and usually both ends of the chain molecule contains free hydroxyl or carboxyl groups.

Such unsaturated polyesterimide has an excellent film-forming ability even with no solvent or a small amount of solvent, and also has excellent storage stability without causing problems such as gelation in a short period of time even when stored in a solution state. are doing.

On the other hand, when used, it can be photocured very well due to the photopolymerizable carbon-carbon double bond based on P-phenylene diacrylic acid in the chain molecule, and it can be cured in a short period of time without using a photosensitizer. It has the advantage of being able to cure over time. Many of the conventionally known photosensitive materials can achieve a practical curing speed without the use of a photosensitizer, and in this respect they can be said to be extremely useful photosensitive materials. Furthermore, the cured film exhibits excellent heat resistance due to the imide bonds within the chain molecules. Further, the adhesion between the cured film and the adherend is good, and there is an advantage that etching treatment on the surface of the adherend, which was conventionally considered indispensable for improving adhesive strength, is not necessary. In addition, this type of coating has excellent properties such as insulation properties, moisture resistance, and chemical resistance, and can ultimately satisfy all of the above-mentioned required properties as a heat-resistant photosensitive material. On the other hand, prior to the completion of the present invention, the inventors had already discovered, together with P-phenylene diacrylic acid or its derivatives, a dibasic acid having an imide bond in the molecule derived from trimellitic acid and a diamine. It has been discovered that an unsaturated polyesterimide obtained by reacting these dibasic acids with a general polyhydric alcohol can be used in combination with an excellent heat-resistant photosensitive material similar to that of the present invention.

However, in this prior invention, if too much of the dibasic acid having an imide bond is used, the photocuring performance of the unsaturated polyesterimide is significantly impaired, and the solubility in organic solvents is also impaired. It was necessary to suppress the amount of the dibasic acid to a small amount of about 0.1 to 0.4 mole based on P-phenylene diacrylic acid or its derivative. On the other hand, the dihydric alcohol having an imide bond in the molecule represented by the above general formula used in the present invention has fewer problems of reducing photocuring ability and solubility as described above.
Therefore, the polyhydric alcohol component can be used in approximately equimolar ratio to P-phenylene diacrylic acid or its derivatives, and the above-mentioned dihydric alcohol having an imide bond can be used alone as the polyhydric alcohol component. In this embodiment, the number of imide bonds contained in the unsaturated polyester imide obtained is greatly increased, and the advantage is that it is possible to provide a photosensitive material with better heat resistance than that of the prior invention. is brought about.

The dihydric alcohol having an imide bond in the molecule represented by the above general formula used in this invention is 1, 2,
It is easily produced by reacting 1 mole of 3,4-butanetetracarboxylic acid with 2 moles of amino alcohol.

Here, the amino alcohols include monoethanolamine, isopropanolamine, butanolamine, cyclohexanolamine, cyclopentanolamine, 2-
Hydroxyethylaniline and the like are used. In addition to the above, in this invention, the above-mentioned dihydric alcohol can be used alone as a polyhydric alcohol component, but other polyhydric alcohols can also be used in combination if necessary. The proportion is 5 to 100 mol% of dihydric alcohol having an imide bond in the molecule, and 0 to 95 mol% of other polyhydric alcohols.
It may be expressed as mol%, and if the amount of dihydric alcohol having an imide bond is too small, heat resistance, moisture resistance, etc. will deteriorate.
Other polyhydric alcohols mentioned above include ethylene glycol, diethylene glycol, triethylene. Other examples include glycerin, trimethylolpropane, tris(2-hydroxyethyl)isocyanurate, and the like.

On the other hand, P- is subjected to an esterification reaction with these polyhydric alcohols.
Phenylene diacrylic acid is a dibasic acid represented by the following structural formula; its derivatives include those with a substituent on the benzene nucleus in the above structural formula, those with both terminal carboxyl groups as lower alkyl esters, etc. - Examples include those modified with groups that exhibit activity as citric acid components against glycols such as rogogenides.

The above P-phenylene diacrylic acid or its derivatives can be used alone as a polybasic acid component, but
If necessary, it is also possible to use other polybasic acids such as chive acid in combination with the above acid components.

However, the amount used should be within a range that does not impair the features of the invention resulting from the use of P-phenylene diacrylic acid or its derivatives, and is appropriately set depending on the type of polybasic acid. The unsaturated polyesterimide according to the present invention contains at least a polyhydric alcohol including a dihydric alcohol represented by the above general formula having an imide bond in the molecule as described above, and at least P-phenylene diacrylic acid or a derivative thereof. It is produced by heat-reacting polybasic acids containing polybasic acids according to a conventional method, and then further heat-reacting them under reduced pressure to achieve a high degree of condensation. It is preferable that such unsaturated polyesterimide has an acid value of 30 or less.

Here, the acid value means the number of potassium hydroxides required to neutralize the carboxylic acid contained in Sample 19. If the acid value is too high, moisture resistance properties may be reduced. The heat-resistant photosensitive material of the present invention contains the above-mentioned unsaturated olopolyesterimide as a main component, and as mentioned above, even this polyesterimide alone can be rapidly photocured. However, if particularly desired, commonly known photosensitizers may be incorporated. It has been found that the addition of such a photosensitizer has almost no adverse effect on the storage stability, which is one of the characteristics of this invention. Examples of photosensitizers include benzoin, benzoin methyl ether,
Examples include carbonyl compounds such as benzoin isopropyl ether, benzyl and benzyl dimethyl ketal, organic sulfur compounds such as benzyl sulfide, halogen compounds, and photoreducible dyes.

The amount of such photosensitizer used is 1 part of unsaturated polyesterimide.
The amount is usually 5 parts by weight or less per 00 parts by weight.
If the amount is too large, the effect on storage stability etc. cannot be ignored. Furthermore, the heat-resistant photosensitive material of this invention is
Due to the properties of P-phenylene diacrylic acid or its derivatives, it has the characteristics of so-called spectral sensitization,
When performing such spectral sensitization, N is added to the material.
- Known sensitizers such as acetyl-4-nitronaphthylamine and 5-nitroacenaphthene can be blended.

This formulation provides sensitivity to the visible region of 400 nm or more, allowing exposure not only to ultraviolet rays but also to tungsten lamps. Furthermore, in this invention, if a known organic peroxide is used as a thermosetting catalyst instead of or together with the photosensitizer, the curing function will be improved when heat treatment is performed as a post-treatment after photocuring. The effect of improving this can be obtained.

In addition to the above-mentioned components, the heat-resistant photosensitive material of the present invention may contain known additives such as fillers and adhesion aids, if necessary.

In addition, for resist materials such as heat-resistant photoresists, small amounts of appropriate organic solvents such as toluene, acetone, and tetrahydrofuran are blended, and vinyl monomers,
A polymerizable unsaturated compound such as a divinyl compound, an acrylic (methacrylic) acid compound, or an unsaturated polyester resin may be blended to reduce the viscosity during film formation. The heat-resistant photosensitive material of the present invention thus obtained has excellent storage stability, and does not gel in a short period of time even when left in liquid or solution form at room temperature.

However, when storing for a long period of time, it is preferable to store it in a dark room or in a cold room, taking into consideration its photosensitivity. On the other hand, when using it, it is usually heated to 50 to 100°C to make it fluid (of course, if it is in a liquid or solution state at room temperature, there is no need to heat it), and then it is coated with a bar coater, applicator, spinner, etc. After coating the adherend, it is photocured by irradiation with actinic rays, and if necessary, a post-heat treatment is performed to further improve heat resistance and adhesion. A cured film can be formed. Examples of this invention will be described below. Example 1 Monoethanolamine 1229 (2 moles) was added to a 50013 four-bottle flask equipped with a stirrer, condenser, and thermometer.
was charged, and 1,2,3,4-butanetetracarboxylic acid 2349 (1 mol) was gradually added over about 30 minutes while stirring at room temperature.

The exothermic temperature at that time was 120°C, and the reaction system became transparent when stirring was continued for about 10 minutes after the addition of the acid. Heating was started from this point, and when the temperature was raised to 210° C. in about 1 hour, 719% of produced water was distilled out. Next 10-2011i
The remaining water was removed by reducing the pressure at 1tH9 to obtain a dihydric}alcohol having an imide bond in the molecule represented by the above general formula. Dihydric alcohol having this imide bond 14.2
9 (0.05 mol), P-phenylene diacrylic acid 10
．． 9f! (0.05 mol) at 180-210°C for 9 hours, approximately 1011mH9, 25-3 mol at 200°C.
An unsaturated polyesterimide was produced by heating for a period of time.

The acid value of this polyesterimide was 21. The obtained unsaturated polyesterimide was used as a heat-resistant photosensitive material of the present invention. Example 23 5.7 g of dihydric alcohol having imide bond of Example 1
(0.02 mol), ethylene glycol 3.1 g (0,
05 mol), P-phenylene diacrylic acid 10.99 (
0.05 mol) was charged, and an unsaturated polyesterimide was prepared in the same manner as in Example 1.

4 The acid value of this polyesterimide was 13. The obtained unsaturated polyesterimide was used as a heat-resistant photosensitive material of the present invention. Example 3 Dihydric alcohol having imide bond of Example 1 2.89
(0.01 mol), 1,6-hexanediol 2.49
(0.02 mol), P-phenylene diacrylic acid 6.5
9 (0.03 mol) was prepared in the same manner as in Example 1 to prepare an unsaturated polyesterimide.

The acid value of this polyesterimide was 17. The obtained unsaturated polyesterimide was used as a heat-resistant photosensitive material of the present invention. The following characteristic tests were conducted using the materials of Examples 1 to 3 above, and the results are shown in the table below.

<Storage Stability> Each material was dissolved and mixed with tetrahydrofuran so that the resin content was 30% by weight, and the mixture was left at room temperature to examine changes in properties.

The number of days during which no gelation was observed and no change in properties was observed is shown in the table. Photocurability> Each material was heated to 8°C to form a uniform liquid, and coated onto a 50 μm copper foil to a thickness of 10 μm using a bar coater.

Using two high-pressure mercury lamps with an input of 30 W/CTIL and a lamp output of 1 Kw, the material was irradiated for 5 minutes from a position 20 crn away to be photocured and the quality of the cured state was examined. Adhesion> The cured film after the photocuring test was 271i! ! A cross cut was made at a T angle, the tape was peeled off, and the number of peeled pieces in 100 cross cut parts was determined.

Heat Resistance> After the photocurability test, the state of the cured film was examined after heat treatment at 150° C. for 120 hours.

Soldering Heat Resistance> After the photocurability test, the state of the cured film after being immersed in a solder bath at 260±5° C. for 10 seconds was examined.

Moisture Resistance> After the photocuring test, the state of the cured film was examined at 40° C. and 90% RH for 120 hours.

Chemical Resistance> After the photocurability test, the state of the cured film was examined after being immersed in each solvent of toluene, tetrahydrofuran, and ethanol at 25° C. for 1 hour.

Claims (1)

[Claims] 1 P-phenylene diacrylic acid or a derivative thereof;
The following general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R represents the residue of an amino alcohol). A heat-resistant photosensitive material whose main component is unsaturated polyesterimide obtained by reaction.